Solid state thermal method for the synthesis of lithium hexafluoro phosphate (LiPF)6 as battery electrolyte

ABSTRACT

The present invention provides a method for the preparation of LiPF 6  (lithium hexafluoro phosphate) wherein equimolar quantities of pure dry AR lithium source such as Li 2 O or Li 2 CO 3  or LiNO 3  is mixed with (very pure dry and AR samples) diammonium hydrogen phosphate in solid state.

FIELD OF THE INVENTION

The present invention relates to a novel process for the preparation of Lithium hexafluoro phosphate (LiPF₆). More particularly, the present invention relates to a novel process for the preparation of Lithium hexafluoro phosphate (LiPF₆) which is useful as a battery electrolyte especially for rocking chair cells and other primary non-aqueous lithium based cells and solid state and solid polymer electrolyte lithium cells.

BACKGROUND OF THE INVENTION

LiPF₆ is a well-known electrolyte for secondary lithium based cells which is difficult to prepare because of very active raw materials like P₂O₅, Li₂O and PF₅ and F₂ gases. There are a few chemical procedures available in literature however, they need careful purification and handling. Moreover, such procedures require a wide range of equipment to operate and prepare this essential chemical for rocking chair or lithium ion or intercalation battery systems.

Metal fluorides of phosphorous viz. MPF₆ where M is Ca, K or Li can be prepared by reacting MF with PF₃. (Paul et. al., Fluorine Chemistry, 56, 1995). Hence,

3MF+5PF₃→3MPF₆+2P

Where M is Ca, K or Cs MPF₆ can be prepared by neutralising HPF₆ with appropriate base viz.,

2HPF₆+Ca(OH)₂→Ca(MF₆)₂+2H₂O

Similarly some of the hexafluorophosphates can be prepared by double decomposition of NH₄PF₆ or KPF₆. (Paul et. al., Fluorine Chemistry, 56, 1995; Fluorine Chemistry, Vol. 5, Simons J. H., 131(1819), 1964; Fluorine Chemistry, Vol. 1, Emelson H. J., 76(219), 1995) LiPF₆ prepared by earlier methods suffer has certain disadvantages like, they need toxic chemicals as reactants, it becomes difficult to handle the chemicals involved, the final product contains unreacted impurities, it is a partial reaction, it needs further steps for preparation and it is not a pure solid state reaction.

OBJECTS OF THE INVENTION

The main object of this present invention is to provide a novel method for the synthesis of (LiPF₆) lithiumhexafluorophosphate as a battery electrolyte.

Another object of this present invention is to provide a complete solid state reaction.

Still another object of this present invention is to avoid many active chemicals which are difficult to handle.

Yet another object of this invention is to avoid obnoxious gases.

Still yet another object of this invention is to get the product without any partial reaction.

These and other objects of the invention are achieved and the problems associated with the prior art are overcome by the process of the invention described below.

SUMMARY OF THE INVENTION

A novel method for the preparation of LiPF₆ (lithium hexafluoro phosphate) is developed where in equimolar quantities of pure dry AR lithium source such as Li₂O or Li₂CO₃ or LiNO₃ is mixed with (very pure dry and AR samples) diammonium hydrogen phosphate and the mixture was heated to 200°-600° C. continuously for 6 hours in an electric furnace. The product was cooled and was then transferred into a dry vessel. The product was a transparent substance which was confirmed by X-ray analysis as LiAsF₆.

Accordingly, the present invention provides a novel solid state thermal process for the synthesis of lithium hexafluoro phosphate (LiPF₆), which comprises of:

(a) mixing a lithium source selected from the group consisting of a lithium oxide, a lithium salt and a combination thereof with diammonium phosphate in equimolar proportions;

(b) heating the mixture in a furnace at a temperature in the range of 150° C. to 600° C. continuously to obtain LiPO₃;

(c) cooling and powdering the LiPO₃

(d) mixing of the powdered product with six to nine times quantitatively of ammonium fluoride and then heating it at a temperature in the range of 150° C. to 200° C. using a furnace continuously for 4-6 hours in a closed Teflon container;

(e) transferring the product to a dry vessel.

In one embodiment of the invention, step (b) above is carried out for a time in the range of 4 to 6 hours.

In an embodiment of the present invention LiPO₃ is mixed with NH₄F in the ratio 1:6-9 to form LiPF₆.

In another embodiment of the present invention, lithium meta phosphate (LiPO₃) is mixed with ammonium fluoride in a ratio of 1:7 and the mixture heated to 200° C. in an electric furnace for 6 hours continuously to get lithium hexafluoro phosphate.

In yet another embodiment of the present invention Li₂CO₃ or Li₂O or LiNO₃ is mixed with diammonium hydrogen phosphate and ammonium fluoride in the molar ratios 1:2:6-9

In another embodiment of the present invention Li₂CO₃ or Li₂O or LiNO₃ is mixed with diammonium hydrogen phosphate and ammonium fluoride in the ratio of 1:1:7.

In yet another embodiment of the present invention, Li₂O or LiNO₃ is mixed with diammonium hydrogen phosphate and ammonium fluoride in the ratio 1:1:7 and the mixture is heated at 200° C. continuously for 12 hours in an electric furnace to obtain LiPF₆.

In an embodiment of the present invention Li₂CO₃ or Li₂O or LiNO₃ is mixed with diammonium phosphate in the ratio 1:1 and then, the product is mixed with NH₄F in the ratio of 1:7 and heated.

In still another embodiment of this invention the temperature is kept between 150-350° C. for the preparation of LiPF₆ when LiNO₃ or Li₂O in the starting material.

In another embodiment of the invention, for Li₂CO₃ the temperature of heating with (NH₄)₂HPO₄ is around 600° C. and subsequently with NH₄F mixed and heating the temperature is kept in between 150-350° C.

In another embodiment of the invention, the reactions occur in solid state.

In yet another embodiment of the invention, the process comprises a two step reaction as follows: $\begin{matrix} (a) \\ {{{2\left( {NH}_{4} \right)_{2}{HPO}_{4}} + {{Li}_{2}O}}\overset{{300{^\circ}\quad {C.}}\quad}{\rightarrow}{{2\quad {LiPO}_{3}} + {4{NH}_{3}} + {3H_{2}O}}} \\ {{{2\left( {NH}_{4} \right)_{2}{HPO}_{4}} + {{Li}_{2}{CO}_{3}}}\overset{{600{^\circ}\quad {C.}}\quad}{\rightarrow}{{2\quad {LiPO}_{3}} + {4{NH}_{3}} + {CO}_{2} + {3H_{2}O}}} \\ {{{2\left( {NH}_{4} \right)_{2}{HPO}_{4}} + {2{LiNO}_{3}}}\overset{{300{^\circ}\quad {C.}}\quad}{\rightarrow}{{2\quad {LiPO}_{3}} + {4{NH}_{3}} + {2{NO}_{2}} + {2H_{2}O} + O_{2}}} \\ {{{(b)\quad {LiPO}_{3}} + {6{NH}_{4}F}}\overset{{> {150{–300{^\circ}}\quad {C.}}}\quad}{\rightarrow}{{LiPF}_{6} + {6{NH}_{3}} + {3H_{2}O}}} \end{matrix}$

In yet another embodiment of this invention a single step process is possible at a temperature>150-300° C.

Li₂O+2 (NH₄)₂HPO₄+12 NH₄F→2 LiPF₆+16NH₃+9H₂O

Li₂CO₃+2 (NH₄)₂HPO₄+12 NH₄F→2 LiPF₆+16NH₃+CO₂+9H₂O

LiNO₃+2 (NH₄)₂HPO₄+12 NH₄F→2 LiPF₆+16NH₃+NO₂+9H₂O

In another embodiment of the present invention, pure dry Li₂O or Li₂CO₃ or LiNO₃ is mixed with twice the quantity of diammonium phosphate i.e., in the molar ratio of 1:2 and the mixture is heated in an electric or muffle furnace for 6 hours at a temperature of 600° C. continuously for Li₂CO₃ and around 300° C. for Li₂O and LiNO₃. The product was dried at 80° C. and was then allowed to react with NH₄F in the molar ratio of 1:>6-8 for 4 hours in an electric furnace continuously at a temperature range of 150-350° C.

In yet another embodiment of this invention all materials are in solid state conditions.

It is a feature of this invention that an electrical furnace can be used for the process.

It is another feature of this invention that a muffle furnace can be used for the process.

In yet another embodiment of this invention a single step process is possible viz., ${{(a)\quad {LiPO}_{3}} + {6{NH}_{4}F}}\overset{{> {150{–300{^\circ}}\quad {C.}}}\quad}{\rightarrow}{{LiPF}_{6} + {6{NH}_{3}} + {3H_{2}O}}$

DETAILED DESCRIPTION OF THE INVENTION

Lithium hexafluoro phosphate, is an essential chemical for rocking chair cells, lithium ion cells or intercalation battery systems. However, the process for preparing this compound by earlier methods is difficult and has many drawbacks.

The present invention relates to a novel solid state thermal process for the preparation of LiPF₆, which overcomes the previous difficulties. It comprises of a solid state reaction of a lithium salt or a lithium oxide or a combination of both with diammonium phosphate in equimolar proportions obtaining a mixture of the two compounds. The mixture is then heated in a furnace at 600° C. and the product obtained is powdered after cooling. It is then mixed with ammonium fluoride six times the quantity of LiPO₃ obtained, from the reaction, and then heated at 200° C. using a furnace continuously for 4-6 hours in a closed Teflon container.

The main advantages of the present invention are that first, there are no side reactions, second a single step or double step process can be possible depending on the method of approach, third, a pure sample of LiPF₆ is obtained, fourth, it is a purely solid state reaction under thermal control as no gases or liquids are used even for the initial reaction, fifth, the purity of the product depends on the purity of the reactants and last, the process is simple, uncomplicated and highly efficient.

The invention will now be described in greater detail with reference to the following examples, which are illustrative and therefore should not be construed as limiting the scope of the present invention in any manner:

EXAMPLE 1

An equimolar mixture of Li₂CO₃ (AR) and (NH₄)2HPO₄ (AR) are ground well and mixed together and heated to 600° C. in an electric/muffle furnace for 6 hours continuously and then product was ground well and mixed with NH₄F (AR) and the mixture was heated again in the electrical furnace/muffle furnace for 4 hours at a temperature of 200° C.

Components Composition First step Li₂CO₃ 0.74 g (NH₄)₂HPO₄ 1.32 g Particle size of the mixture 5 mμ. Temperature 600° C. Time 6 hours Second step NH₄F 2.6 g Temperature 600° C. Time 4 hours Nature of the product transparent Efficiency of the process >90%

EXAMPLE 2

An equimolar mixture of Li₂O (AR) and (NH₄)₂HPO₄ (AR) are ground well and mixed together and heated to 600° C. in an electric/muffle furnace for 6 hours continuously and then product was ground well and mixed with NH₄F (AR) and the mixture was heated again in the electrical furnace/muffle furnace for 4 hours at a temperature of 200° C.

Components Composition First step Li₂O 0.3 g (NH₄)₂HPO₄ 1.32 g Particle size of the mixture 5 mμ. Temperature 400° C. Time 6 hours Second step NH₄F 2.6 g Temperature 200° C. Time 4 hours Nature of the product transparent Efficiency of the process >90%

EXAMPLE 3

An equimolar mixture of LiNO₃ (AR) and (NH₄)₂HPO₄ (AR) are ground well and mixed together and heated to 400° C. in an electric/muffle furnace for 6 hours continuously and then product was ground well and mixed with NH₄F (AR) and the mixture was heated again in the electrical furnace/muffle furnace for 4 hours at a temperature of 200° C.

Components Composition First step LiNO₃ 0.69 g (NH₄)₂HPO₄ 1.32 g Particle size of the mixture 5 mμ. Temperature 400° C. Time 6 hours Second step NH₄F 2.6 g Temperature 200° C. Time 4 hours Nature of the product transparent Efficiency of the process >90%

EXAMPLE 4

An equimolar mixture of lithium meta phosphate (LiPO₃) and ammonium fluoride in the ratio 1:>6-8 is taken and then mixed and ground well and then heated in an electric/muffle furnace then the temperature of heating was continued for 4 hours at 200° C. till the final product was formed.

Components Composition First step LiNO₃ 0.69 g (NH₄)₂HPO₄ 1.32 g Particle size of the mixture 5 mμ. Temperature 600° C. Time 6 hours Second step NH₄F 2.6 g Temperature 600° C. Time 4 hours Nature of the product transparent Efficiency of the process >90%

EXAMPLE 5

Li₂O, (NH₄)₂HPO₄ (AR) and NH₄F mixture is taken in the ratio of 1:2:7 and the mixed material is heated in an electric/muffle furnace for 6 hours at a temperature of 300° C. continuously.

Components Composition Li₂O 0.30 g (NH₄)₂HPO₄ 1.32 g NH₄F 2.60 g Particle size of the mixture 5 mμ. Temperature 300° C. Time 6 hours Nature of the product transparent Efficiency of the process >90%

EXAMPLE 6

Li₂CO₃, (NH₄)₂HPO₄ (AR) and NH₄F mixture is taken in the ratio of 1:2:7 and the mixed material is heated in an electric/muffle furnace for 6 hours at a temperature of 300° C. continuously.

Components Composition Li₂CO₃ 0.74 g (NH₄)₂HPO₄ 1.32 g NH₄F 2.60 g Particle size of the mixture 5 mμ. Time 6 hours Temperature 600° C. Nature of the product transparent Efficiency of the process >90%

EXAMPLE 7

LiNO₃, (NH₄)₂HPO₄ (AR) and NH₄F mixture is taken in the ratio of 1:2:7 and the mixed material is heated in an electric/muffle furnace for 4 hours at a temperature of 300° C. continuously

Components Composition LiNO₃ 0.69 g (NH₄)₂HPO₄ 1.32 g NH₄F 2.60 g Particle size of the mixture 5 mμ. Time 4 hours Temperature 300° C. Nature of the product transparent Efficiency of the process >90% 

We claim:
 1. A solid state thermal process for synthesis of lithium hexafluoro phosphate (LiPF₆), which comprises the steps of: (a) mixing a lithium source selected from the group consisting of a lithium oxide, a lithium salt and a combination thereof with diammonium phosphate in equimolar proportions to obtain a first mixture; (b) heating the first mixture in a furnace at a first temperature in the range of 150° C. to 600° C. continuously to obtain product lithium meta phosphate (LiPO₃); (c) cooling and powdering the product LiPO₃; and (d) mixing the powdered product LiPO₃ with six to nine times quantitatively of ammonium fluoride to form a second mixture and then heating the second mixture at a second temperature in the range of 150° C. to 200° C. to obtain lithium hexafluoro phosphate.
 2. A process as claimed in claim 1 wherein step (b) is carried out for a time in the range of 4 to 6 hours.
 3. A process as claimed in claim 1 wherein lithium meta phosphate is mixed with ammonium fluoride in a molar ratio of 1:7 and the second mixture is heated to 200° C. in an electric furnace for 6 hours continuously to obtain lithium hexafluoro phosphate.
 4. A process as claimed in claim 1 wherein Li₂CO₃ or Li₂O or LiNO₃ is mixed with diammonium hydrogen phosphate and ammonium fluoride in a molar ratio of 1:2:6-9.
 5. A process as claimed in claim 1 wherein Li₂CO₃ or Li₂O or LiNO₃ is mixed with diammonium hydrogen phosphate and ammonium fluoride in a molar ratio of 1:1:7.
 6. A process as claimed in claim 1 wherein Li₂O or LiNO₃ is mixed with diammonium hydrogen phosphate and ammonium fluoride in a molar ratio of 1:1:7 and the second mixture is heated at 200° C. continuously for 12 hours in an electric furnace to obtain LiPF₆.
 7. A process as claimed in claim 1 wherein Li₂CO₃ or Li₂O or LiNO₃ is mixed with diammonium phosphate in a molar ratio of 1:1 and the product LiPO₃ is mixed with NH₄F in a molar ratio of 1:7.
 8. A process as claimed in claim 1 wherein the first temperature is between 150-350° C. when LiNO₃ or Li₂O is the lithium source.
 9. A process as claimed in claim 1 wherein for Li₂CO₃ the first temperature is about 600° C. and the second temperature is between 150-350° C.
 10. A process as claimed in claim 1 wherein the reactions occur in solid state.
 11. A process as claimed in claim 1 wherein the process comprises a two step reaction as follows: $\begin{matrix} (a) \\ {{{2\left( {NH}_{4} \right)_{2}{HPO}_{4}} + {{Li}_{2}O}}\overset{{300{^\circ}\quad {C.}}\quad}{\rightarrow}{{2\quad {LiPO}_{3}} + {4{NH}_{3}} + {3H_{2}O}}} \\ {{{2\left( {NH}_{4} \right)_{2}{HPO}_{4}} + {{Li}_{2}{CO}_{3}}}\overset{{600{^\circ}\quad {C.}}\quad}{\rightarrow}{{2\quad {LiPO}_{3}} + {4{NH}_{3}} + {CO}_{2} + {3H_{2}O}}} \\ {{{2\left( {NH}_{4} \right)_{2}{HPO}_{4}} + {2{LiNO}_{3}}}\overset{{300{^\circ}\quad {C.}}\quad}{\rightarrow}{{2\quad {LiPO}_{3}} + {4{NH}_{3}} + {2{NO}_{2}} + {2H_{2}O} + O_{2}}} \\ {{{(b)\quad {LiPO}_{3}} + {6{NH}_{4}F}}\overset{{> {150{–300{^\circ}}\quad {C.}}}\quad}{\rightarrow}{{LiPF}_{6} + {6{NH}_{3}} + {3H_{2}O}}} \end{matrix}$


12. A process as claimed in claim 1 wherein the process comprises a single step reaction at a temperature greater than 150 to 300° C. Li₂O+2(NH₄)₂HPO₄+12 NH₄F→2 LiPF₆+16NH₃+9H₂O Li₂CO₃+2(NH₄)₂HPO₄+12 NH₄F→2 LiPF₆+16NH₃+CO₂+9H₂O Li₂NO₃+2(NH₄)₂HPO₄+12 NH₄F→2 LiPF₆+16NH₃+NO₂+9H₂O.
 13. A process as claimed in claim 1 wherein pure dry Li₂O or Li₂CO₃ or LiNO₃ is mixed with twice the quantity of diammonium phosphate to obtain the first mixture and the first mixture is heated in an electric or muffle furnace for 6 hours at a temperature of 600° C. continuously for Li₂CO₃ and about 300° C. for Li₂O and LiNO₃ and the product Li₂CO₃ is then dried at 80° C. and reacted with NH₄F in a molar ratio of 1:>6-8 for 4 hours in an electric furnace continuously at a temperature range of 150-350° C.
 14. A process as claimed in claim 1 wherein all materials are in solid state conditions.
 15. A process as claimed in claim 1 wherein the furnace is an electrical furnace.
 16. A process as claimed in claim 1 wherein the furnace is a muffle furnace.
 17. A process as claimed in claim 1 wherein the process comprises a single step reaction as follows: ${{(a)\quad {LiPO}_{3}} + {6{NH}_{4}F}}\overset{{> {150{–300{^\circ}}\quad {C.}}}\quad}{\rightarrow}{{LiPF}_{6} + {6{NH}_{3}} + {3H_{2}{O.}}}$


18. A process as claimed in claim 1, wherein heating the second mixture at the second temperature includes using a furnace continuously for 4-6 hours in a closed Teflon container.
 19. A process as claimed in claim 1, further comprising the step of (e) transferring the lithium hexafluoro phosphate to a dry vessel. 